Abstract We investigated the temporal response of four dental impression materials, namely three siloxanes Imprint 4, Flexitime, Aquasil and one polyether Impregum. The null hypothesis was that the nominal working times are confirmed by instrumental laboratory tests. We also aimed to identify alternative techniques with strong physical-chemical background for the assessment of temporal response. Traditional characterization was carried out by shark fin test device and durometer at both ambient and body temperature. Additionally, Fourier-transform infrared spectroscopy was performed at room temperature. From shark fin height and Shore hardness versus time the working time and the setting time of the materials were evaluated, respectively. These were in reasonable agreement with the nominal values, except for Impregum, which showed longer working time. Spectroscopy confirmed the different character of the two types of materials, and provided for Imprint 4 and Aquasil an independent evaluation of both evolution times, consistent with the results of the other techniques. Shark fin test and durometer measurements showed deviations in setting time, low sensitivity to temperature for Flexitime, and longer working time at higher temperature for Impregum. Deviations of working time appear in operating conditions from what specified by the manufacturers. Fourier-transform infrared spectroscopy can provide insight in the correlation between material properties and their composition and structure. View Full-Text